Azo compounds containing two 6-hydroxypyrid-2-one coupling component radicals the nitrogen atoms of which are linked by a biscationic radical

ABSTRACT

Compounds of the formula ##STR1## wherein each A is independently linear or branched C 2-6  alkylene or linear or branched C 3-6  alkylene substituted by hydroxy, 
     each D is independently the radical of a diazo component of the benzene, azobenzene or naphthalene series,  E is a divalent radical attached to each --N.sup.⊕ R 3  R 4  -- radical through an aliphatic carbon atom, 
     each R 1  is independently hydrogen, C 1-4  alkyl, cyclohexyl, phenyl or phenyl(C 1-2  alkyl), 
     each R 2  is independently hydrogen, cyano, --COOR 5 , --CONR 6  R 7  or ##STR2##  wherein R 5  is hydrogen, C 1-4  alkyl or phenyl(C 1-2  alkyl), 
     each of R 6  and R 7  is independently hydrogen or C 1-4  alkyl, 
     each R 8  is independently C 1-4  alkyl, and r is 0, 1, 2 or 3, 
     each R 3  is independently C 1-4  alkyl or C 1-4  alkyl monosubstituted by halo, cyano, hydroxy or phenyl, 
     each R 4  is independently hydrogen, C 1-4  alkyl or C 1-4  alkyl monosubstituted by halo, cyano, hydroxy or phenyl, 
     each An.sup.⊖  is a non-chromophoric anion, and n is 0, 1, 2, 3, 4, 5 or 6, 
     with the proviso that the negative charges of the An.sup.⊖ &#39;s balance the positive charge of each cationic group of the molecule not balanced by the negative charge of an anionic group of the molecule, compositions containing them and their use for dyeing and printing hydroxy group- or nitrogen-containing organic substances.

This is a continuation of application Ser. No. 07/417,361, filed Oct. 5,1989, now abandoned.

The invention relates to basic pyridone disazo to tetrakisazo compounds,a process for their production and their use in dyeing and printingprocesses.

There is provided according to the invention compounds of formula I andmixtures thereof ##STR3## in which each R₁ independently is hydrogen,C₁₋₄ alkyl, cyclohexyl, phenyl or phenyl (C₁₋₂ alkyl)

each R₂ independently is hydrogen, --CN, --COOR₅, --CONR₆ R₇, ##STR4##R₅ is hydrogen, C₁₋₄ alkyl or phenyl (C₁₋₂ alkyl); each R₆ and R₇independently is hydrogen or C₁₋₄ alkyl;

m is 1, 2 or 3;

each R₈ independently is C₁₋₄ alkyl;

each R₃ independently is C₁₋₄ alkyl, unsubstituted or monosubstituted byhalogen, cyano, hydroxy or phenyl;

each R₄ independently is hydrogen or has a significance of R₃,independent of R₃ ;

each A independently is C₂₋₆ alkylene or C₃₋₆ alkylene substituted byhydroxy;

E is a divalent bridging member attached to each N⊕₃ R₄ -- Radicalthrough an aliphatic carbon atom;

each D, independently, is the radical of a diazo component selected fromthe benzene, azobenzene, or naphthalene series which may contain awater-solubilizing group selected form SO₃ H, COOH and SO₂ NH₂ ;

An⊖ is a non-chromophoric anion; and

n is the number of negative charges which are necessary to compensatethe positive charges present in the molecule which are not compensatedby any anionic groups in D. Preferably n is 0 or an integer from 1 to 6.

Preferably number of cationic groups in a compound of the formula Iexceeds the number of anionic groups in both groups D.

Preferably there are no anionic groups (SO₃ H or COOH) other than thosein a group D present in a compound of formula I.

Any gorup capable of being linear or branched is linear or branchedunless indicated to the contrary.

When a hydroxy-substituted alkyl or alkylene group is bonded tonitrogen, the hydroxy group is preferably located at a C-atom which isnot directly bonded to nitrogen (i.e. is not attached to the α-carbonatom).

Preferably halogen is fluorine, chlorine or bromine, more preferablychlorine or bromine and especially chlorine.

Preferably R₁ is R_(1a) where each R_(1a) independently is methyl,ehtyl, cyclohexyl, phenyl or benzyl.

More preferably R₁ is R_(1b) where each R_(1b) independently is methylor ethyl.

More preferably R₁ is methyl.

Preferably R₂ is R_(2a) where each R_(2a) independently is hydrogen,cyano, --COOR_(5a), --CONR_(6a) R_(7a), ##STR5## where R_(5a), R_(6a)and R_(7a) are defined below.

More preferably R_(2b) where each R_(2b) independently is hydrogen, 13COOR_(5a), --CONHR_(7a), ##STR6##

Most preferably R_(2c) where each R_(2c) independently is ##STR7##

Preferably when R₃ or R₄ is unsubstituted alkyl, it is C₁₋₂ alkyl, morepreferably methyl. Preferably when R₃ or R₄ is substituted alkyl, it isC₂₋₃ alkyl which is monosubstituted by chlorine or hydroxy.

Preferably R₃ is R_(3a) where each R_(3a) independently is methyl, ethylor C₂₋₃ alkyl monosubstituted by hydroxy or chlorine.

More preferably R₃ is R_(3b) where each R_(3b) independently is methyl,ethyl or 2-hydroxyethyl.

Most preferably R₃ is methyl.

Preferably R₄ is R_(4a) where each R_(4a) independently is hydrogen or asignificance of R_(3a) independent of R_(3a).

More preferably R₄ is R_(4b) where each R_(4b) independently hydrogen ora significance of R_(3b), independent of R_(3b).

Most preferably R₄ is methyl.

Preferably R₅ is R_(5a) where R_(5a) is hydrogen, methyl or ethyl.

Preferably R₆ and R₇ are R_(6a) and R_(7a) which independently arehydrogen or C₁₋₂ alkyl.

Preferably R₈ is methyl.

Preferably when A is alkylene, it is C₂₋₄ alkylene (more preferably--(CH₂)_(p) -- in which p=2, 3 or 4; --CH₂ --CH(CH₃)--; CH₂ --CH(CH₂CH₃)--; or --CH(CH₃)--CH(CH₃)-- of which --(CH₂)_(p') --, in which p'=2or 3 is most preferred).

Preferably when A is hydroxy-substituted alkylene, it is hydroxy-C₃₋₄alkylene.

Preferably A is A₁ where each A₁ independently is C₂₋₄ alkylene ormonohydroxy-substituted C₃₋₄ alkylene.

More preferably A is A₂ where each A₂ independently is C₂₋₄ alkylene.

Most preferably A is A₃ where each A₃ independently is --(CH₂)_(p') --,where _(p') is 2 or 3.

Preferably E is E_(1a) where E_(1a) is unsubstituted C₂₋₄ alkylene,monohydroxy-substituted C₃₋₄ alkylene, C₂₋₆ alkylene interrupted by--O--, --NR₉ -- or ##STR8## where R₁₀ is as defined below; ormonohydroxy- or dihydroxy-substituted C₃₋₈ alkylene which is interruptedby --O--, --NR₉ -- or ##STR9## in which R₉ is hydrogen or C₁₋₆ alkyl and

R₁₀ is hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy.

More preferably E is E_(2a) is unsubstituted C₂₋₃ alkylene,monohydroxy-substituted C₃₋₄ alkylene or --Qa--X--Qa; where each Qa,independently is unsbustituted C₁₋₃ alkylene or monohydroxy-substitutedC₃₋₄ alkylene- , and X is --NR_(9a) -- or ##STR10## where R_(9a) ishydrogen or C₁₋₄ alkyl and R_(10a) is hydrogen, chlorine, methyl ormethoxy.

Most preferably E is E_(3a) where E_(3a) is C₂₋₃ alkylene,monohydroxy-substituted C₃₋₄ alkylene or --CH₂ --C₆ H₄ --CH₂ --.

Preferably D is D_(a) where each D_(a) independently is a group##STR11## in which R₁₀ is defined as above; and

R₁₁ is hydrogen, halogen, nitro, C₁₋₄ alkyl, --COOH, ##STR12## in whichQ₁ is a direct bond or a bridging group;

Q₂ is C₂₋₈ alkylene, hydroxy-substituted C₃₋₆ alkylene, C₁₋₆=alkylene-(1,3 or 1,4-phenylene)-- or 1,3- or 1,4-phenylene-;

R₁₂ is hydrogen or C₁₋₄ alkyl;

q is 0 or 1;

R₁₃ and R₁₄ independently are hydrogen, unsubstituted C₁₋₆ alkyl; C₂₋₆alkyl monosubstituted by hydroxy or cyano; phenyl unsubstituted orsbustitited byone to three substituents selected from chlorine, C₁₋₄alkyl and C₁₋₄ alkoxy; or phenyl (C₁₋₄ alkyl), the phenyl ring isunsubstituted or substituted by one to three sustituents selected fromchlorine, C₁₋₄ alkyl and C₁₋₄ alkoxy; unsubstituted C₅₋₆ cycloalkyl orC₅₋₆ cycloalkyl which is substituted by one to three C₁₋₄ alkyl groups;

or --NR₁₃ R₁₄ forms a 5- or 6-membered ring which may contain 1 or 2additional hetero atoms selected from nitrogen, oxygen and sulfur andwhich ring is unsubstituted or substituted by one or two C₁₋₄ alkylgroups;

R₁₅ and R₁₆, independently of one another, have one of the significancesof R₁₃ and R₁₄ independent of R₁₃ and R₁₄, except hydrogen; and

R₁₇ is C₁₋₄ alkyl or benzyl; or

--⊕R₁₅ R₁₆ R₁₇ form a pyridinium ring which is unsubstituted orsubstituted by one or two methyl groups or a 5- or 6-membered ring whichmay contain 1 or 2 additional hetero atoms selected from nitrogen,oxygen and sulfur, the cationic nitrogen atom having an R₁₇ group, whichring is unsubstituted or substituted by one or two C₁₋₄ alkyl groups;

An⊖ is a non-chromophoric anion;

R₁₈ is hydrogen or SO₃ H; and

R₁₉ is hydrogen, SO₃ H, COOH, or SO₂ NH₂.

More preferably D is a group D_(b) where each D_(b) independently is agroup ##STR13## in which R_(10a) is hydrogen, chlorine, methyl ormethoxy; and R_(11a) is hydrogen, chlorine, nitro, methyl, methoxy##STR14## in which q is 0 or 1;

Q_(1a) is a direct bond, --CO--, 13 *N(R_(12a))--NHCOCH₂ -- or --SO₂ --;in which the * atom is bonded to a C-atom of the benzene ring (to whichR₁₁ is attached),

Q_(2a) is C₂₋₃ alkylene,

R_(12a) is hydrogen or methyl,

R_(13a) and R_(14a), independently of one another, are hydrogen, methylor ethyl,

R_(15a) and R_(16a), independently of one another, are methyl or ethyl;

R_(17a) is methyl, ethyl or benzyl, or

R_(13a) and R_(14a) or R_(15a) and R_(16a) together with the N-atom towhich they are attached, form a piperidine, peiperazine or morpholinering, or R_(15a), R_(16a) and R_(17a) together with the N-atom to whichthey are attached, form a pyridinium ring which may be substituted bymethyl.

More preferably D is a group D_(c), where each D_(c), independently, is##STR15## in which R_(11b) is hydrogen, chlorine, nitro, methyl,methoxy, phenyl, --NH--phenyl, --SO₂ NH₂, --CON(R_(12a))--Q_(2a)--NR_(13a) R_(14a), or ##STR16## and the other symbols are as definedabove.

Most preferably D is D_(d) where each D_(d) independently is ##STR17##where the symbols are as defined above.

Preferred compounds of formula I are those of formula Ia ##STR18## inwhich when D_(b) contains one anionic group, the total number of thecationic groups present in the molecule exceeds the number of theanionic groups in both groups D_(b).

Preferably in compounds of formula Ia, R_(1a) is R_(1b) and R_(2a) isR_(2b) (more preferably where R_(1a) is methyl and R_(2a) is R_(2c)).

Preferably in compounds of formula Ia A₂ is A₃.

Preferably in compounds of formula Ia E_(2a) is E_(3a).

Preferably in compounds of formula Ia D_(b) is D_(c) or D_(d).

Preferably in compounds of formula Ia R_(3b) and R_(4b) are methyl.

Preferably the compound of formula Ia is symmetrical around E_(2a).

Further according to the invention, there is provided a process forpreparing compounds of formula I, comprising

(a) reacting two moles of the same compound of formula II, or one moleof two different compounds of formula II ##STR19## with the one mole ofan E-yielding compound thereby quaternising the NR₃ R₄ group of eachcompound of formula II; or

(b) when it is desired to prepare a compound of formula I in which bothD are identical, coupling two moles of the diazotised amine of formulaIII

    D--NH.sub.2                                                (III)

with one mole of a compound of formula IV ##STR20## in which the symbolsare as defined above.

Diazotisation and coupling reactions can be carried out in accordancewith known methods. Preferably coupling is effected at a slightly acidicpH.

The condensation of two compounds of formula II is conveniently carriedout at an elevated temperature of 40° to 70° C., preferably 50° to 60°C., and in an alkaline medium, preferably at pH 9 to 10.

A compound of formula I may be isolated from the reaction mixture in aknown manner or may be used per se in the form of the solution obtained,i.e. without isolation from the reaction mixture.

A compound of formula IV, used as a coupling component, may be obtainedby an analogous process to that for preparing a compound of formula I,comprising reacting two moles of a compound of formula V or one mole oftwo different compounds of formula V ##STR21## with one mole of anE-yielding compound thereby quaternising the NR.sub. R₄ group of eachcompound of formula IV.

The compounds of formulae II, III and V used to synthesize the compoundsof formulae I and IV are known or may be obtained by known methods fromknown compounds.

The compounds of formula I may be in the form of water-soluble salts andsome can also form inner salts. An anion An⊖, that can be introduced byreacting a protonatable N-atom and/or quaternary ammonium group withorganic or inorganic acid, may be for example one of the following:

Chloride, bromide, iodide, sulphate, bisulphate, methyl sulphate, ethylsulphate, amino sulphate, hydrogen sulphate, perchlorate,benzenesulphonate, oxalate, maleinate, acetate, methoxyacetate, formate,propionate, lactate, succinate, tartrate, malate, methanesulphonate, theanions of acids such as boric acid, citric acid, glycolic acid,diglycolic acid or adipic acid or addition products of ortho-boric acidwith polyalcohols, e.g. cis-polyols.

The compounds of formula I in water-soluble salt form can be used asdyestuffs for dyeing or printign hydroxy group-containing ornitrogen-containing organic substrates. They can for example be used fordyeing or printing cationically dyeable materials such as single ormixed polymers of acrylonitrile, acid-modified polyamide or polyesterfibres; leather, cotton or bast fibres such as hemp, flax, sisal, jute,coir fibres and straw; regenerated cellulose fibres, glass fibres andpaper.

The compounds of the formula I can also be used, for example, for dyeingor printing fibres, filaments or textiles produced therefrom, whichconsist of or contain cellulose material, e.g. cotton, according toknown methods. One preferred method known for dyeing cotton is aconventional exhaust process, for example from a long or short bath andat room temperature to boiling temperature. One preferred method foreffecting printing employs impregnation with a printign paste which canbe prepared by known methods.

The compounds of the formula I can also be used for the dyeing orprinting of leather by known methods and in particular of low-affinitytypes of leather which have undergone vegetable retanning.

The compounds of formula I are especially suitable for dyeing orprinting paper or paper products, e.g. for the production of sized orunsized, wood-free or in particular wood-containing paper (so-calledmechanical wood pulp) in pulp form such as in the sizing press. Dyeingand printing of paper may be effected by known methods. A preferredmethod for the dyeing of paper uses a dipping process.

The dyeings and prints obtained, and in particular the paper dyeings andpaper prints, have good fastness during usage.

The compounds of formula I may be used directly (in powder form or as asolution) as dyestuffs, or may be used in the form of dyeingpreparations. The processing into stable liquid, preferably aqueous, andsolid dyeing preparations mayb e carried out by known methods. Forexample, suitable liquid preparations may be obtined by dissolving thedyestuff of formula I in suitable solvents such as mineral acids ororganic acids, e.g. hydrochloric acid, sulphuric acid, phosphoric acid,formic acid, acetic acid, lactic acid, glycolic acid, methane sulphonicacid and citric acid, or further solvents such as fomamide,dimethylformamide, urea; glycols and their ethers which are used in amixture with water, optionally with an assistant, e.g. a stabilizer.Such preparations may be produced for example as described in FrenchPatent Specification No. 1,372,030.

A preferred liquid preparation is, for example, as follows (parts are byweight):

100 parts of a compound of formula I,

1-100, preferably 1-10, parts of an inorganic salt,

1-100 parts of an organic acid such as formic, acetic, lactic, citric,propionic and/or methoxyacetic acid,

100-800 parts of water,

0-500 parts of a solvent assistant (e.g. glycols such as ethyleneglycol, propylene glycol, di- or triethylene glycol, hexylene glycol;glycol ethers such as methyl cellosolve, methyl carbitol, butylpolyglycol; urea, formamide and/or dimethylformamide).

Similarly, the compounds of formula I can be processed in known mannerinto solid, preferably granulated dyeing preparations, advantageously bygranulating as described in French Patent Specification No. 1,581,900.

A preferred composition for solid preparation is, for example, asfollows (all parts are by weight):

100 parts of a compound of formula I,

1-100, preferably 1-10, part of an inorganic salt,

0-800 parts of a standardising agent (preferably non-ionic such asdextrin, sugar, grape sugar and urea).

The solid preparation may contain up to 10% residual moisture.

The compounds of formula I have good solubility properties and areespecially notable for their good solubility in cold water. As a resultof their high substantivity, the dyestuffs are absorbed practicallyquantitatively and thus have good build-up. When producing sized andunsized paper, the waste water is practically colourless or is onlyslightly coloured. The dyestuffs can be added to the paper pulpdirectly, i.e. without predissolving, as a dry powder or granulate,without any reduction in brillance or in the yield of colour.

The compounds of formula I are preferably used however in solution or asliquid-aqueous dyeing preparations.

Compared with unsized paper dyeings, the sized paper dyeings show noloss of depth.

The compounds of formula I can also be used for dyeing in soft waterwith a full yield of color. The compounds of formula I do not mottleespecially when dyed on wood-containing paper; they are not inclined toproduce two-sided effects on paper and are substantially insensitivetowards fillers and pH variations.

The dyed papers and especially those dyed purely with a cationiccompound of the formula I have a high level of fastness to bleeding.They have very good west fastness not only to water, but also to milk,fruit juies, sweetened mineral water, soap water, tonic water, sodiumchloride solution, and urine. In addition, they have good alcoholfastness.

Paper which has been dyed with the compounds of formula I can bebleached both by oxidation and by reduction, which is important for there-use of broke and old paper.

Fibrous materials containing mechanical wood pulp are dyed by thepresent dyestuffs in a good and even quality.

The following examples illustrate the invention. In the examples, allparts and percentages are by weight unless indicated to the contrary andall temperatures are given in degrees celsius.

EXAMPLE 1

(a) 143.5 parts of6-hydroxy-4-methyl-1-(3'-dimethylamino)propyl-3-pyridiniumpyridone-(2)-betaine,400 parts of water and 25 parts of 30% hydrochloric acid are placed in areaction flask. This is heated to 50°-60° and then 27.8 parts ofepichlorohydrin are added dropwise to the reaction solution. The pH ismaintained at between 9 and 10 by adding ca. 20 parts of 30% sodiumhydroxide solution. After stirring for about 30 minutes, the pH remainsunchanged. An aqueous solution of the pyridone compound of formula 1b##STR22## may be used further as a coupling component without isolation.

(b) 39.4 parts of 4-amino-1,1'-azobenzene are diazotised by a knownmethod in a solution containing hydrochloric acid and are coupled at pH4 with 77.6 parts of the coupling component of formula 1b produced under(a). The dyestuff of formula 1a result ##STR23##

It can be used without isolation as a solution for dyeing paper.

The yellowish-orange paper dyeings obtained have good fastness.

EXAMPLE 2

13.3 parts of the compound of formula 2b, ##STR24## produced by a knownmethod by diazotising and coupling of 4-amino-1,1'-azobenzene with6-hydroxy-4-methyl-1-(3'-dimethylamino)propyl-3-pyridiniumpyridone-(2)-betaine,are made into a paste in 200 parts of water. A pH of 9-10 is set by theaddition of sodium hydroxide solution. 2.2 parts ofα,α'-dichloro-p-xylene are added to this reaction mixture which isheated to 60°. After stirring for three hours, the reaction isterminated. The resultant dyestuff is of formula 2a ##STR25## and isobtained by precipitating with acetone and subsequently filtering. Itdyes paper in orange shades. The dyeings have a good level of fastness.

EXAMPLES 3

If in step b of Example 1, 18.6 parts of aminobenzene are used in placeof the 39.4 parts of 4-amin-1,1-azobenzene, a compound of formula 3a##STR26## results. This can be used as a dyestuff without the need toisolate the dyestuff. The resultign paper dyeings are yellow and havegood fastness properties, especially good wet fastness properties.

EXAMPLES 4 to 84

Further compounds of formula 4a ##STR27## in which the symbols are asdefined in Table 1 below are produced analogously to the methoddescribed in Example 1 or 2, from appropriate corresponding startingmaterials.

Further, compounds of formula 4b ##STR28## in which the symbols are asdefined in Table 2 are produced analogously to the method described inExample 1 or 2, from appropriate corresponding starting materials.

An⊖ signifies a non-chromophoric anion, as originally existing in thereaction medium, preferably C1⊖ or CH₃ COO⊖.

When dyed on paper, these dyestuffs produce yellow-orange to orangedyeings, which have a high level of fastness, especially regarding wastewater and wet fastness.

Examples 4 to 24, 33, 34, 38, 39 and 71-84 produce yellow dyeings onpaper. The remaining Examples produce yellowish - orange dyeings onpaper.

In Examples 14-18 inner salts may be formed.

In the following Tables E₁ to E₄ are as follows:

E₁ is --CH₂ --CH(OH)--CH₂ --

E₂ is --CH₂ --CH₂ --.

E₃ = ##STR29## E₄ = ##STR30##

                  TABLE 1                                                         ______________________________________                                        Ex. No.                                                                              D                        R.sub.3                                                                              E                                      ______________________________________                                         4                                                                                                            CH.sub.3                                                                             E.sub.2                                 5     "                        "      E.sub.3                                 6     "                        C.sub.2 H.sub.5                                                                      E.sub.1                                 7                                                                                    ##STR31##               CH.sub.3                                                                             E.sub.1                                 8     "                        "      E.sub.3                                 9                                                                                    ##STR32##               "      E.sub.1                                10     "                        C.sub.2 H.sub.5                                                                      E.sub.1                                11                                                                                    ##STR33##               CH.sub.3                                                                             E.sub.1                                12     "                        "      E.sub.3                                13     "                        "      E.sub.4                                14                                                                                    ##STR34##               "      E.sub.1                                15     "                        C.sub.2 H.sub.5                                                                      E.sub.2                                16     "                        CH.sub.3                                                                             E.sub.3                                17                                                                                    ##STR35##               CH.sub.3                                                                             E.sub.1                                18     "                        "      E.sub.2                                19                                                                                    ##STR36##               "      E.sub.1                                20     "                        C.sub.2 H.sub.5                                                                      E.sub.3                                21                                                                                    ##STR37##               CH.sub.3                                                                             E.sub.1                                22                                                                                    ##STR38##               "      E.sub.1                                23     "                        C.sub.2 H.sub.5                                                                      E.sub.1                                24     "                        CH.sub.3                                                                             E.sub.3                                25                                                                                    ##STR39##               CH.sub.3                                                                             E.sub.1                                26     "                        C.sub.2 H.sub.5                                                                      E.sub.1                                27     "                        CH.sub.3                                                                             E.sub.2                                28     "                        "      E.sub.3                                29     "                        "      E.sub.4                                30                                                                                    ##STR40##               "      E.sub.1                                31     "                        C.sub.2 H.sub.5                                                                      E.sub.2                                32     "                        CH.sub.3                                                                             E.sub.3                                33                                                                                    ##STR41##               "      E.sub.1                                34     "                        "      E.sub.3                                35                                                                                    ##STR42##               CH.sub.3                                                                             E.sub.1                                36     "                        "      E.sub.2                                37     "                        "      E.sub.4                                38                                                                                    ##STR43##               "      E.sub.1                                39     "                        C.sub.2 H.sub.5                                                                      E.sub.3                                40                                                                                    ##STR44##               CH.sub.3                                                                             E.sub.1                                41     "                        "      E.sub.3                                42                                                                                    ##STR45##               "      E.sub.1                                43     "                        C.sub.2 H.sub.5                                                                      E.sub.1                                44                                                                                    ##STR46##               CH.sub.3                                                                             E.sub.1                                45     "                        "      E.sub.3                                46                                                                                    ##STR47##               "      E.sub.1                                47     "                        "      E.sub.4                                48                                                                                    ##STR48##               "      E.sub.1                                49     "                        "      E.sub.3                                50                                                                                    ##STR49##               CH.sub.3                                                                             E.sub.1                                51     "                        "      E.sub.2                                52                                                                                    ##STR50##               "      E.sub.2                                53     "                        C.sub.2 H.sub.5                                                                      E.sub.1                                54     "                        CH.sub.3                                                                             E.sub.4                                55                                                                                    ##STR51##               "      E.sub.1                                56     "                        "      E.sub.3                                57                                                                                    ##STR52##               "      E.sub.1                                58     "                        "      E.sub.2                                59     "                        "      E.sub.3                                60                                                                                    ##STR53##               "      E.sub.1                                61     "                        "      E.sub.3                                62     "                        "      E.sub.4                                63                                                                                    ##STR54##               "      E.sub.1                                64     "                        C.sub.2 H.sub.5                                                                      E.sub.3                                65                                                                                    ##STR55##               CH.sub.3                                                                             E.sub.1                                66     "                        "      E.sub.3                                67                                                                                    ##STR56##               CH.sub.3                                                                             E.sub.4                                68                                                                                    ##STR57##               "      E.sub.1                                69     "                        "      E.sub.2                                70     "                        "      E.sub.3                                ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Ex. No.  R                   R.sub.3                                                                              E                                         ______________________________________                                        71       H                   CH.sub.3                                                                             E.sub.3                                   72       H                   C.sub.2 H.sub.5                                                                      E.sub.3                                   73       H                   CH.sub.3                                                                             E.sub.1                                   74       H                   "      E.sub.2                                   75       4-CH.sub.3          "      E.sub.3                                   76       "                   C.sub.2 H.sub.5                                                                      E.sub.3                                   77       "                   CH.sub.3                                                                             E.sub.1                                   78       3-SO.sub.2 NH.sub.2 "      E.sub.3                                   79       "                   C.sub.2 H.sub.5                                                                      E.sub.3                                   80       "                   CH.sub.3                                                                             E.sub.1                                   81       4-CONH(CH.sub.2).sub.3 N(C.sub.2 H.sub.5).sub.2                                                   "      E.sub.1                                   82       "                   "      E.sub.3                                   83       "                   "      E.sub.2                                   84       4-CH.sub.3          "      E.sub.4                                   ______________________________________                                    

The uses of the dyestuffs described are illustrated in the followingDyeing Examples.

DYEING EXAMPLE A

70 parts of chemically bleached sulphite cellulose of pinewood and 30parts of chemically bleached sulphite cellulose of birchwood are groundin a Hollander in 2000 parts of water. 0.5 parts of the dyestuffsolution of the compound of formula 1a (as produced in Example 1) areadded to this mass, or 0.1 parts of the dyestuff of Example 2 aresprinkled in. After mixing for 20 minutes, apper is produced therefom.The absorbent paper obtained in this way is dyed yellowish-orange. Thewaste water is colourless.

DYEING EXAMPLE B

0.5 parts of the dyestuff solution of the compound of formula 1a (asproduced in Example 1) or 0.2 parts of the compound of formula 2a (asproduced in Example 2) are added to 100 parts of chemically bleachedsulphite cellulose, which have been ground in a Hollanander in 2000parts of water. After thorough mixing for 15 minutes, sizing takes placein the usual way with rosin size and aluminum sulphate. Paper which isproduced from this material has a yellowish-orange shade and possessesgood waste water and wet fastness.

DYEING EXAMPLE C

An absorbent length of unsized paper is drawn through a dyestuffsolution of the following composition at 40°-50°:

0.5 parts of the compound of formula 1a (as produced in Example 1) or0.2 parts of the compound of formula 2a (as produced in Example 2)

0.5 parts of starch and

99.0 (99.3) parts of water.

The excess dyestuff solution is squeezed out through two rollers. Thedried length of paper is dyed yellowish-orange and has a high level offastness.

Dyeing may also take place analogously to Examples A to C, using thedyestuffs of Examples 3-62 or liquid preparations thereof. Theyellowish-orange to orange paper dyeings obtained have a high level offastness.

DYEING EXAMPLE D

1.0 part of the compound of formula 2a (as produced in Example 2) isdissolved at 40° in 4000 parts of softened water. 100 parts ofpremoistened cotton fabric are added to the bath, which is heated in 30minutes to boiling temperature. The bath is held at boiling temperaturefor one hour, whereby the water which evaporates is replaced from timeto time. The dyed fabric is then removed from the liquor, rinsed withwater and dried. The dyestuff is absorbed practically quantitatively onthe fibres and the dyebath is alsmot colourless. A yellowish-orangedyeing with good fastness is obtained.

DYEING EXAMPLE E

100 parts of freshly tanned and neutralised chrome grain leather aredrummed for 30 minutes in a vat containing a bath of 250 parts of waterof 55° and 0.5 parts of the compound of formula 2a (as produced inExample 2) and are treated in the same bath for a further 30 minuteswith 2 parts of an anionic fat liquor based on sulphonated train oil.The leathers are dried and finished in the usual way. An evenly dyedleather in orange shades is obtained.

Further low affinity, vegetable-retanned leathers may similarly be dyedby known methods.

DYEING EXAMPLE F

A dry substance consisting of 60% mechanical wood pump and 40%unbleached sulphite cellulose is mxied in a Hollander with sufficientwater and ground to a grinding degree of 40°SR (Schopper-Rieglerdegree), such that the dry content is a little above 2.5%; the mixtureis subsequently adjusted with water to exactly 2.5% dry content of thicksubstance.

200 parts of this thick substance are mixed with 5 parts of a 0.25%aqueous solution of the compound of formula 1a (as produced inExample 1) and stirred for ca. 5 minutes. After adding 2% rosin size and4% alum (based on dry substance), homogeneous stirring again takes placefor a few minutes. The pulp is diluted with ca. 500 parts of water to700 parts and paper sheets are produced therefrom in known manner bypassing through a sheet former. The paper sheets have an intensivelyyellowish-orange shade.

DYEING EXAMPLE G

15 parts of old paper (woody), 25 parts of bleached mechanical wood pulpand 10 parts of unbleached sulphate cellulose are impacted in a pulperto a 3% aqueous pulp suspension. The pulp suspension is diluted to 2% ina dyeing vat. Then, (calculated on total dry fibres) 5% kaolin and 0.6parts of a 5% acetic solution of the compound of formula 1a (as producedin example 1) are added to this suspension after one another whilststirring. After 20 minutes, 1% (calculated on dry weight of the totalfibres) of a rosin size dispersion is added to the pump in the mixingvat. The homogeneous pulp suspension is adjusted to pH 5 with alum onthe paper machine shortly before operating.

In this way, orange-dyed bag paper of 80 g/m² with a machine finish isproduced on the paper machine. The dyed paper has very good bleedingfastness in accordance with DIN 53 991. The paper can be almost totallydecolourised with hypochlorite.

Dyeing Examples A to G can be repeates using instead of the compound offormula 1a or 2a an appropriate amount of any one of Examples 3 to 84.In all cases, the waste water shows only a slight concentration ofdyestuff.

What is claimed is:
 1. A compound of the formula ##STR58## or a mixturethereof, wherein each A is independently linear or branched C₂₋₆alkylene or linear or branched C₃₋₆ alkylene substituted by hydroxy,eachD is independently the radical of a diazo component of the benzene,azobenzene or naphthalene series, E_(1a) is linear or branched C₂₋₄alkylene; linear or branched C₃₋₄ alkylene monosubstituted by hydroxy;linear or branched C₂₋₆ alkylene interrupted by --O--, --NR₉ -- or##STR59## or linear or branched C₃₋₈ alkylene monosubstituted ordisubstituted by hydroxy and interrupted by --O--, --NR₉ -- or ##STR60##wherein R₉ is hydrogen or C₁₋₆ alkyl, andR₁₀ is hydrogen, halo, C₁₋₄alkyl or C₁₋₄ alkoxy, each R₁ is independently hydrogen, C₁₋₄ alkyl,cyclohexyl, phenyl or phenyl(C₁₋₂ alkyl), each R₂ is independentlyhydrogen, cyano, --COOR₅, --CONR₆ R₇ or ##STR61## wherein R₅ ishydrogen, C₁₋₄ alkyl or phenyl(C₁₋₂ alkyl),each of R₆ and R₇ isindependently hydrogen or C₁₋₄ alkyl, each R₈ is independently C₁₋₄alkyl, and r is 0, 1, 2 or 3, each R₃ is independently C₁₋₄ alkyl orC₁₋₄ alkyl monosubstituted by halo, cyano, hydroxy or phenyl, each R₄ isindependently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkyl monosubstituted byhalo, cyano, hydroxy or phenyl each An⊖ is a non-chromophoric anion, andn is , 1, 2, 3, 4, 5 or 6,with the proviso that the negative charges ofthe An⊖'s balance the positive charge of each cationic group of themolecule not balanced by the negative charge of an anionic group of themolecule.
 2. A compound according to claim
 1. 3. A compound according toclaim 2 wherein each D is independently the radical of a diazo componentof the benzene, azobenzene or naphthalene series containing asubstitutent selected from sulfo, carboxy and sulfamoyl.
 4. A compoundaccording to claim 2 wherein each halo is fluoro, chloro or bromo, withthe provisos that (i) the number of cationic groups exceeds the numberof anionic groups, and (ii) each hydroxy substituent of each alkyl groupand alkylene radical bonded to a nitrogen atom is bonded to a carbonatom that is not directly bonded to a nitrogen atom.
 5. A compoundaccording to claim 2 wherein each R₁ is independently methyl, ethyl,cyclohexyl, phenyl or benzyl.
 6. A compound according to claim 2 whereineach R₂ is independently hydrogen, cyano, --COOR_(5a), ##STR62## whereineach of R_(5a), R_(6a) and R_(7a) is independently hydrogen, methyl orethyl.
 7. A compound according to claim 2 whereineach R₃ isindependently methyl, ethyl or 2-hydroxyethyl, and each R₄ isindependently hydrogen, methyl, ethyl or 2-hydroxyethyl.
 8. A compoundaccording to claim 2 whereineach A is independently is linear orbranched C₂₋₄ alkylene or linear or branched C₃₋₄ alkylenemonosubstituted by hydroxy.
 9. A compound according to claim 2 whereineach D is independently ##STR63## wherein R₁₁ is hydrogen, halo, nitro,C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy, --Q₁ --(NR₁₂ --Q₂)_(q) --NR₁₃ R₁₄,--Q₁ --(NR₁₂ --Q₂)_(q) --NR⊕₁₅ R₁₆ R₁₇, ##STR64## R₁₈ is hydrogen orsulfo, and R₁₉ is hydrogen, sulfo, carboxy or sulfamoyl,wherien Q₁ is adirect bond, --CO--, --NR_(12a) --NHCOCH₂ -- or --SO₂ --, whereinR_(12a) is hydrogen or methyl, and the * denotes the atom that is bondedto a carbon atom of the ring to which R₁₁ is bonded, Q₂ is linear orbranched C₂₋₈ alkylene; linear or branched C₃₋₆ alkylene substituted byhydroxy; linear or branched C₁₋₆ alkylene-1,3-phenylene; linear orbranched C₁₋₆ alkylene-1,4-phenylene; 1,3-phenylene or 1,4-phenylene,eachR₁₀ is independently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₁₂is hydrogen or C₁₋₄ alkyl, each of R₁₃ and R₁₄ is independentlyhydrogen; C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by hydroxy or cyano;phenyl; phenyl substituted by one to three substituents selected fromchloro, C₁₋₄ alkyl and C₁₋₄ alkoxy; phenyl(C₁₋₄ alkyl); phenyl(C₁₋₄alkyl) the phenyl ring of which is substituted by one to threesubstituents selected from chloro, C₁₋₄ alkyl and C₁₋₄ alkoxy; Chd5-6cycloalkyl; or C₅₋₆ cycloalkyl substituted by one to three C₁₋₄ alkylgroup; or --NR₁₃ R₁₄ is piperidino; piperazino; morpholino; orpiperidino, piperazino or morpholino substituted by one or two C₁₋₄alkyl gruops, each of R₁₅ and R₁₆ is independently C₁₌₆ alkyl; C₂₋₆alkyl monosubstituted by hydroxy or cyano; phenyl; phenyl substituted byone to three substituents selected from chloro, C₁₋₄ alkyl and C₁₋₄alkoxy; phenyl(C₁₋₄ alkyl); phenyl(C₁₋₄ alkyl) the phenyl ring of whichis substituted by one to three substituents selected from chloro, C₁₋₄alkyl and C₁₋₄ alkoxy; C₅₋₆ cycloalkyl; or C₅₋₆ cycloalkyl substitutedby one to three C₁₋₄ alkyl groups, R₁₇ is C₁₋₄ alkyl or benzyl, or ⊖--NR₁₅ R₁₆ R₁₇ is pyridinium; methylpyridinium; dimethylpyridinium;N-R₁₇ -piperidinium; N-R₁₇ -piperazinium; N-R₁₇ -morpholinum; or N-R₁₇-piperidinium, N-R₁₇ -piperazinium or N-R₁₇ -morpholinium substituted byone or two C₁₋₄ alkyl groups, wherein R₁₇ is C₁₋₄ alkyl or benzyl, and qis 0 or
 1. 10. A compound according to claim 9 having the formula##STR65## wherien each A₂ is independently linear or branched C₂₋₄alkylene,each D_(b) is independently ##STR66## wherein R_(11a) ishydrogen, chloro, nitro, methyl, methoxy, carboxy, ##STR67## wherienQ_(1a) is a direct bond, --CO--, --NR_(12a) --NHCOCH₂ -- or --SO₂ --,whereinthe * denotes the atom that is bonded to a carbon atom of thering to which R_(11a) is bonded, Q_(2a) is linear or branched C₂₋₃alkylene, each of R_(13a) and R_(14a) is independently hydrogen, methylor ethyl, or --NR_(13a) R_(14a) is piperidino, piperazino or morpholino,each of R_(15a) and R_(16a) is independently methyl or ethyl, andR_(17a) is methyl, ethyl or benzyl, or --NR⊕_(15a) R_(16a) R_(17a) ispyridinium, methylpyridinium, N-R_(17a) -piperidinium, N-R_(17a)-piperazinium or N-R_(17a) -morpholinium, wherein R_(17a) is methyl,ethyl or benzyl, andq is 0 or 1, R₁₈ is hydrogen or sulfo, and R₁₉ ishydrogen, sulfo, carboxy or sulfamoyl, E_(2a) is linear or branched C₂₋alkylene; linear or branched C₃₋₄ alkylene monosubstituted by hydroxy;or --Qa--X--Qa--, wherein eachQa is independently linear or branchedC₁₋₃ alkylene or linear or branched C₃₋₄ alkylene monosubstituted byhydroxy, and X is --NR_(9a) -- or ##STR68## wherein R_(9a) is hydrogenor C₁₋₄ alkyl, each R_(1a) is independently methyl, ethyl, cyclohexyl,phenyl or benzyl, each R_(2a) is independently hydrogen, cyano,--COOR_(5a), --CONR_(6a) R_(7a) or ##STR69## wherein each of R_(5a),R_(6a) and R_(7a) is independently hydrogen, methyl or ethyl, andr is 0,1, 2 or 3, each R_(3b) is independently methyl, ethyl or 2-hydroxyethyl,each R_(4b) is independently hydrogen, methyl, ethyl or 2-hydroxyethyl,and n is 0, 1, 2, 3, 4, 5 or 6, wherein each R_(10a) is independentlyhydrogen, chloro, methyl or methoxy, R_(12a) is hydrogen or methyl, andeach An⊖ is a non-chromophoric anion,with the provisos that (i) thenegative charges of the An⊖'s balance the positive charge of eachcatnionic group of the molecule not balanced by the negative charge ofan anionic group of the molecule, and (ii) when a D_(b) contains oneanionic group, the total number of the cationic groups present in themolecule exceeds the number of the anionic groups in both D_(b) groups.11. A compound according to claim 10 with the proviso that any hydroxysubstituent of an alkylene radical bonded to a nitrogen atom is bondedto a carbon atom that is not directly bonded to a nitrogen atom.
 12. Acompound according to claim 10 whereineach A₂ is independently--(CH₂)_(p') --, each D_(b) is independently ##STR70## wherein R_(11b)is hydrogen, chloro, nitro, methyl, methoxy, phenyl, phenylamino,sulfamoyl, --CO--NR_(12a) --Q_(2a) --NR_(13a) R_(14a) or --CO--NR_(12a)--Q_(2a) --NR_(15a) R_(16a) R_(17a),E_(2a) is linear or branched C₂₋₃alkylene, C₃₋₄ alkylene monosubstituted by hydroxy or --CH₂--phenylene--CH₂ --, each R_(1a) is independently methyl or ethyl, eachR_(2a) is independently hydrogen, --COOR_(5a), --CONHR_(7a), pyridiniumor methylpyridinium, and each R_(3b) and R_(4b) is methyl.
 13. Acompound according to claim 12 whereinthe A₂ 's are identical,the D_(b)'s are identical, the R_(1a) 's are identical, and the R_(2a) 's areidentical.
 14. A compound according to claim 12 whereineach R_(1a) ismethyl, each R_(2a) is independently pyridinium or methylpyridinium,each R₁₈ is hydrogen, and each R₁₉ is hydrogen.
 15. A compound accordingto claim 14 whereinthe A₂ 's are identical, the D_(b) 's are identical,and the R_(2a) 's are identical.
 16. A compound according to claim 15with the proviso that any hydroxy substitutent of an alkylene radicalbonded to a nitrogen atom is bonded to a carbon atom that is notdirectly bonded to a nitrogen atom.
 17. A compound according to claim 16having the formula ##STR71## wherein each An⊖ is a non-chromophoricanion.
 18. A compound according to claim 17 wherien each An⊖ is chlorideor acetate.
 19. A storage-stable, aqueous liquid dye compositioncontaining a compound according to claim 1 in water-soluble salt form.